Page 1of38 S1 Supporting Information for A stability study of hypervalent tellurium compounds in aqueous solutions. Cleverson R. Princival, 1 Marcos. V. L. R. Archilha, 1 Alcindo A. dos Santos, 1 Maurício P. Franco, 1 Ataualpa A. C. Braga, 1 André F. Rodrigues-Oliveira, 1 Thiago C. Correra, 1 Rodrigo L. O. R. Cunha* ,2 and João V. Comasseto* ,1,3 . 1 Instituto de Química, Universidade de São Paulo, São Paulo-SP, Brazil. 2 Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André-SP, Brazil. 3 Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo, Diadema-SP, Brazil. CONTENTS Supplemental figures S2 Chemistry S3 Stability study of hypervalent compounds of tellurium¨ S7 NMR spectra S8 HRMS-ESI-(-) spectra S27 Theoretical calculations details S31 Scheme S1 S31 Table S1 S31 Cartesian Coordinates S32 References S38
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Page 1of38
S1
Supporting Information for
A stability study of hypervalent tellurium compounds
in aqueous solutions.
Cleverson R. Princival,1Marcos. V. L. R. Archilha,1 Alcindo A. dos Santos,
1Maurício P.
Franco,1Ataualpa A. C. Braga,
1André F. Rodrigues-Oliveira,
1 Thiago C. Correra,
1Rodrigo L. O. R.
Cunha*,2
and João V. Comasseto*,1,3
.
1Instituto de Química, Universidade de São Paulo, São Paulo-SP, Brazil.
2 Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, Santo André-SP, Brazil.
3Instituto de Ciências Ambientais, Químicas e Farmacêuticas, Universidade Federal de São Paulo,
Diadema-SP, Brazil.
CONTENTS
Supplemental figures S2
Chemistry S3
Stability study of hypervalent compounds of tellurium¨ S7
NMR spectra S8
HRMS-ESI-(-) spectra S27
Theoretical calculations details S31
Scheme S1 S31
Table S1 S31
Cartesian Coordinates S32
References S38
Page 2of38
S2
SUPLEMENTAL FIGURES
Figure S1: (A) 125
Te NMR spectrum and (B) HRMS-ESI-(-) spectrum of AS101 after treated with
propylene glycol.
Figure S2: HRMS-ESI-(-) spectrum of AS101 compound after treatment with 5 equivalents of
ethanol.
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S3
Chemistry
General Chemical methods. Chemical reagents were purchased from Sigma Aldrich. The course of
the reactions was monitored by thin layer chromatography (TLC) on 0.20 mm silica gel 60 F254
plates (Merck, Germany), then visualized with an UV lamp. Nuclear magnetic resonance spectra
(NMR) were recorded on Bruker AC 200 spectrometer (Bruker BioSpin GmbH, Rheinstetten,
Baden-Wurttemberg, Germany) operating at 200, 50 and 63 MHz for 1H,
13C and
125Te NMR,
respectively. CDCl3 and DMSO-d6 were used as solvents and as internal references,
tetramethylsilane (TMS) for 1H NMR, CDCl3 for
13C NMR and diphenylditelluride for
125Te NMR.
Data for NMR spectra are reported as follows: chemical shift (δ ppm), multiplicity (s = singlet, br s =
broad singlet, d = doublet, t = triplet, q = quartet, dd = doublet of doublets, m = multiplet), coupling
constant (Hz), integration.
Microwave reactions were performed with a CEM Discover Synthesis Unit (CEM Co., Matthews,
NC, USA), with a continuous focused microwave power delivery system in a glass vessel (10 or 35
mL) sealed with Teflon cap, under magnetic stirring.
All high resolution mass spectra were acquired in a q-ToF spectrometer Maxis 3G Bruker Daltonics.
Prior to experiments all dry solvents were previously degassed and the concentrations of working
samples in each experiment were of 1 x 10-4
and 1 x 10-5
mol/L.
Syntheses procedures
Preparation of tellurium tetrachloride
In a 50 mL round bottomed flask equipped with a Vigreux column (25 cm), a reflux condenser and a
drying tube, was placed elemental tellurium (200 mesh) previously dried overnight in an oven at 100
°C (3.82 g, 30 mmol) and SO2Cl2 (7.5 mL, 90 mmol). The system was placed into the oven of a
microwave apparatus and then it was irradiated for 4 h at 65 ºC and at 100 W. After this time all the
tellurium powder was consumed and the excess of SO2Cl2 was removed by distillation under
vacuum, leaving behind a white solid which was submitted to high vacuum and heating and then
used for further reactions without purification. Yield: 7.59 g (94%) 1,2
.
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S4
Preparation of p-methoxyphenyltellurium trichloride
In a glass pressure resistant tube (35 mL) equipped with a magnetic stirring bar were placed tellurium
tetrachloride prepared as described for 1 (1.02 g, 8 mmol) and neat anisole (0.87 mL, 8 mmol). The tube was
closed and placed in the oven of a microwave apparatus and then irradiated for 3 min at 50 o C and at 100 W,
after cooling to room temperature. The yellow solid obtained was recrystallized from acetic acid.Yield: 2.34 g
Te NMR spectrum (63 MHz, DMSO-d6 and basic buffer pH = 8 after 6 days at room
temperature) of dichloro (E)-1-(1-chloro-2-(4-methoxyphenyltellanyl)vinyl) cyclohexanol8a.
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S27
Figure S40:125
Te NMR spectrum (63 MHz, DMSO-d6 and acid buffer pH = 5.5 after 48 hours at
room temperature) of dichloro (E)-1-(1-chloro-2-(4-methoxyphenyltellanyl)vinyl) cyclohexanol8a.
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S28
HRMS-ESI-(-) SPECTRA
Figure S41: HRMS-ESI-(-) spectrum of AS101 compound after treatment with two equivalents of
water.
Figure S42: HRMS-ESI-(-) spectrum of AS101 compound after treatment with 100 equivalents of
water.
Figure S43:HRMS-MS-ESI-(-) spectrum of AS101 compound after treatment with two equivalents
of water.
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S29
Figure S44:HRMS-ESI-(-) spectrum of AS101 compound after treatment with 5 equivalents of
ethanol followed by addition of 10 equivalents of water.
Figure S45: HRMS-ESI-(-) spectrum of AS101 compound after treatment with 5 equivalents of
ethanol followed by addition of 100 equivalents of water.
Figure S46: HRMS-ESI-(-) spectrum of AS101 compound after treatment with two equivalents of
propylene glycol.
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S30
Figure S47: HRMS-ESI-(-) spectrum of tellurate 7 after treatmentwith PBS after 30 days at 25 °C.
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S31
THEORETICAL CALCULATIONS
Scheme S1. Hydrolysis of compounds AS101 (first line), 7 (second line) and 8b (third line) with one equivalent of water and Free Gibbs Energy is given at the right side of the reaction. Table S1. Atomic charges from NPA of Tellurium and the atoms bonded to the center atom.
Compound Atomic charges
Te Oaxial Otrans-Cl Caryl Colefin Cltrans-Cl Cltrans-O
AS101 +1.894 -0,839 -0,870 - - -0.600 and
-0.585
-0,648
7 +1.450 - - -0.436 - -0.562, 0.561, -0.558 and -
0.557
-
8b +1.565 - - -0.419 -0.397 -0.573 and
-0.558
-
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CARTESIAN COORDINATES:
Compound AS101
Potential Energy = -1617.85242666 Eh
Free Gibbs Energy = -1617.824634 Eh
Te 0.005048 0.160760 -0.456530
Cl 2.633858 0.070940 -0.368062
Cl -0.044827 2.545271 0.754654
Cl -2.600479 0.089624 -0.304780
O -0.011855 -1.839534 -0.775776
O 0.021472 -0.410937 1.452161
C -0.336206 -2.544070 0.425088
H -1.427230 -2.580962 0.550528
H 0.048782 -3.563235 0.332795
C 0.320019 -1.811644 1.568583
H 1.408860 -1.951830 1.555565
H -0.078093 -2.124613 2.536760
Compound7
Potential Energy = -2195.15824132 Eh
Free Gibbs Energy = -2195.078993 Eh
Te 1.459557 -0.084796 -0.002711
C -0.652264 0.135335 0.002202
C -1.228599 1.408750 0.000323
C -1.453205 -1.003425 0.004049
C -2.607992 1.533104 -0.001318
H -0.612830 2.302937 -0.003427
C -2.838626 -0.884131 0.005863
H -1.009246 -1.994322 0.005368
C -3.418695 0.389485 0.002198
H -3.073547 2.513661 -0.005828
H -3.445209 -1.781937 0.009347
Cl 1.180733 -1.883790 -1.895418
Cl 1.600229 1.835973 -1.776792
Cl 1.200125 -1.990193 1.785133
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Cl 1.588059 1.725680 1.884743
O -4.759512 0.610810 0.001257
C -5.607757 -0.538919 0.008836
H -5.444390 -1.139030 0.909296
H -6.627024 -0.156067 0.003770
H -5.441278 -1.153906 -0.880880
Compound 8b
Potential Energy = -2005.29845772 Eh
Free Gibbs Energy = -2005.102111 Eh
Te -0.756160 0.154733 -1.080853
Cl -1.034497 2.718300 -0.503829
Cl -0.457746 -2.377567 -1.647632
C 1.234988 0.300375 -0.373071
C 1.529415 1.045394 0.772819
C 2.245956 -0.339781 -1.082554
C 2.838970 1.134496 1.209805
H 0.741818 1.539776 1.334984
C 3.566219 -0.250458 -0.648296
H 2.022343 -0.925237 -1.969228
C 3.862634 0.486460 0.502615
H 3.087147 1.698533 2.103383
H 4.343961 -0.754532 -1.210191
O 5.114389 0.628207 1.011670
C 6.177135 -0.037140 0.327391
H 6.287131 0.343768 -0.692752
H 7.078304 0.181752 0.897977
H 6.009866 -1.118523 0.303324
C -1.751587 -0.353225 0.744526
C -1.222541 -1.121123 1.704633
H -1.829164 -1.361086 2.573362
Cl 0.318198 -1.875655 1.776940
C -3.208226 0.103942 0.912334
C -3.877428 0.477630 -0.402610
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H -4.936242 0.674530 -0.213073
H -3.456093 1.389513 -0.838263
H -3.811828 -0.337009 -1.131262
C -3.283073 1.252234 1.911961
H -4.329418 1.535815 2.067479
H -2.853194 0.951088 2.871458
H -2.739268 2.126681 1.544460
O -3.892525 -1.045681 1.459324
H -4.785976 -0.750537 1.684271
Water
Potential Energy = -76.4342601688 Eh
Free Gibbs Energy = -76.430505 Eh
O 0.000000 0.000000 0.119041
H 0.000000 0.757837 -0.476165
H 0.000000 -0.757837 -0.476165
HCl
Potential Energy = -460.782707817 Eh
Free Gibbs Energy = -460.793995 Eh
Cl 0.000000 0.000000 0.071483
H 0.000000 0.000000 -1.215209
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Ethylene glycol
Potential Energy = -230.250218450 Eh
Free Gibbs Energy = -230.192497 Eh
O -1.483274 -0.538694 0.205107
H -1.040372 -1.346270 -0.085665
C -0.713798 0.559558 -0.283608
H -0.682425 0.542691 -1.381932
H -1.238832 1.467494 0.022953
C 0.684357 0.580979 0.268569
H 1.191143 1.497112 -0.064982
H 0.657006 0.583845 1.365957
O 1.368277 -0.579928 -0.208197
H 2.210101 -0.639115 0.258627
Compound [TeOCl3]-
Potential Energy = -1464.01247078 Eh
Free Gibbs Energy = -1464.044042 Eh
Te 0.000211 0.345329 -0.129010
Cl -0.001134 -2.145329 0.161818
Cl 2.652274 0.338332 -0.261480
Cl -2.651768 0.339393 -0.261641
O -0.000039 0.874022 1.606332
Compound 7_OH
Potential Energy = -1810.78582219 Eh
Free Gibbs Energy = -1810.691264 Eh
Te -1.533318 0.014923 -0.223436
C 0.573897 0.157573 -0.127944
C 1.193728 1.320734 -0.593543
C 1.335758 -0.898898 0.361944
C 2.576209 1.414069 -0.580147
H 0.605257 2.153374 -0.965593
C 2.725152 -0.814250 0.373032
H 0.853100 -1.799014 0.731391
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C 3.346628 0.346457 -0.101458
H 3.074553 2.309968 -0.937218
H 3.305018 -1.650307 0.747365
Cl -1.362544 -1.038118 2.394208
Cl -1.726359 2.465188 0.744772
Cl -1.249078 -2.427385 -1.211790
O 4.694917 0.527805 -0.137005
C 5.512757 -0.540639 0.340406
H 5.356458 -1.448696 -0.250437
H 6.540730 -0.200433 0.223920
H 5.312455 -0.747321 1.396536
O -1.314992 0.816469 -2.071027
H -2.193541 0.947307 -2.459013
Compound 8b_OH
Potential Energy = -1620.92324848 Eh
Free Gibbs Energy = -1620.714221 Eh
Te 0.787143 -0.659138 -0.996803
Cl 1.112881 -2.548638 1.096632
C -1.185746 -0.446816 -0.249644
C -1.445792 -0.412922 1.122693
C -2.222618 -0.317209 -1.167513
C -2.743396 -0.230647 1.570170
H -0.637491 -0.511865 1.842100
C -3.532266 -0.139008 -0.723795
H -2.024952 -0.335095 -2.235116
C -3.791472 -0.091381 0.649176
H -2.962406 -0.186575 2.632651
H -4.329803 -0.039014 -1.451061
O -5.030555 0.087911 1.185089
C -6.118467 0.242364 0.273799
H -6.237372 -0.648555 -0.350674
H -7.005520 0.376929 0.890869
H -5.975939 1.122182 -0.361772
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C 1.740598 0.809961 0.242224
C 1.191167 1.993818 0.536235
H 1.754759 2.713479 1.123421
Cl -0.347269 2.618882 0.075496
C 3.169326 0.542456 0.733704
C 3.889958 -0.525107 -0.076489
H 4.932167 -0.574483 0.251430
H 3.451886 -1.516509 0.077611
H 3.881466 -0.286190 -1.144761
C 3.154355 0.187452 2.215424
H 4.179573 0.038129 2.571102
H 2.693175 0.992910 2.794205
H 2.590846 -0.734487 2.384302
O 3.865838 1.798795 0.554989
H 4.748091 1.678404 0.932506
O 0.366319 0.729038 -2.433686
H 0.747956 0.388045 -3.256307
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REFERENCES
(1) Petragnani, N.; Mendes, S. R.; Silveira, C.; Tetrahedron Lett. 2008, 49, 2371-2372.
(2) Princival, C.; Dos Santos A, A.; Comasseto, J. V. J.; Braz. Chem. Soc., 2015, 26, 832-836.
(3) Cunha, R. L. R. O.; Omori, A. T.; Castelani, P.; Toledo, F. T.; Comasseto, J. V.; .J.